1,1'-ferrocenediyl-10,10'-(1,2-ethanediyl)bis[4-methylene-1,7-dioxa-4,10-diazacyclododecane]LiClO4 | 167709-05-9

• 英文名称: 1,1'-ferrocenediyl-10,10'-(1,2-ethanediyl)bis[4-methylene-1,7-dioxa-4,10-diazacyclododecane]LiClO4
• CAS: 167709-05-9
• 化学式: C₃₀H₄₈FeN₄O₄*ClO₄*Li
• 分子量: 690.974
• InChiKey: PVZKRSGXOQZXKK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  1,1'-ferrocenediyl-10,10'-(1,2-ethanediyl)bis[4-methylene-1,7-dioxa-4,10-diazacyclododecane] 、 lithium perchlorate 以 氘代乙腈 为溶剂， 生成 1,1'-ferrocenediyl-10,10'-(1,2-ethanediyl)bis[4-methylene-1,7-dioxa-4,10-diazacyclododecane]LiClO4
  参考文献：
  名称：

  Complexation of Na+ in Redox-Active Ferrocene Crown Ethers, a Structural Investigation, and an Unexpected Case of Li+ Selectivity

  摘要：

  The synthesis of several ferrocene crown ethers is described, which were designed tb selectively coordinate and recognize electrochemically small group I ions sandwiched between two 12-membered crown ether rings. The reactions of the [1,1'-ferrocenediylbis(methylene)]bis[pyridinium] salt [Fcdiyl(py)(2)(2+)] with diaza-12-crown-4 [H(N-2-12-C-4)H], aza-12-crown-4 [H(N-12-C-4)], and 1,2-ethanediylbis(1,7-dioxa-4,10-diazacyclododecane) [C(2)H(4)diyl-((N-2-12-C-4)H)(2)] yielded the respective ferrocene crown ethers 1,1 '':1',1'''-bis(ferrocenediyl)bis[4,10-bis(methylene)-1,7-dioxa-4,10-diazacyclododecane)] 10-diazacyclododecane)] Fcdiyl(N-2-12-C-4)(2)Fcdiyl] (3), [Fcdiyl(N-12-C-4)(2)] (2), and [Fcdiyl(N-2-12-C-4)(2)(C(2)H(4)diyl)] (4). Complexation of group 1 ions was evidenced by NMR, cyclic voltammetry, FAB mass spectrometry, and picrate extraction experiments. This last techniques was used to determine a complexation selectivity of 4 for Li+/Na+ approximate to 20:1. The redox potentials of the ligands 2, 3, and 4 were determined by cyclic voltammetry; addition of Li+ or Na+ results in anodic shifts of the redox potentials of up to 100 mV for (4Na+ and 140 mV for(4Li+. The X-ray crystal structures of [(2)NaClO4](2), [(2)NaBPh(4)](2), 3, 3 . 2HClO(4), 4, and (4)NaI were determined to understand the coordination behavior of these ligands and the metal ion selectivities displayed. The determining factor for the stability of the metal complexes is the orientation of the plane of the cyclopentadienyl (Cp) ring with respect to the CpCH(2)-N vector. In metal ion or proton complexes torsion angles of close to 90 degrees are preferred, which allow the equal participation of all donor atoms in the coordination of a cation. This property, however, prevents the complexation of Na+ or Li+ within the cavity formed by 3. Replacing one 1,1'-ferrocenediylbis(methylene) group in 3 by a sterically more suitable C2H4 bridge results in 4 and allows formation of the Na+-sandwich (4)NaI. In this complex strain is apparent, which leads to the preferential coordination of Li+ by 4. The results obtained in this study make it possible to set up a correlation of the anodic shifts Delta E of the iron redox potentials upon complexation of Na+ by ferrocene crown ethers and the inverse distance Fe-Na+ as determined by crystal structure analysis Delta E congruent to 1/(Fe-Na+). This indicates that crystal structures of metal complexes of ferrocene crown ethers can serve as reasonable models for the corresponding species in solution.

  DOI：

  10.1021/ic00119a018